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Solid state structure of WCl2(OCH2CH2CH2CH2PPh2)2 and π-bonding ability of alkoxide in chelating PO ligand
Inorganica Chimica Acta 334 (2002) 455 /458 www.elsevier.com/locate/ica
Note
Solid state structure of WCl2(OCH2CH2CH2CH2PPh2)2 and pbonding ability of alkoxide in chelating P O ligand /
Myung-Young Lee a, Sang Ook Kang b, Youhyuk Kim a,* a
Department of Chemistry, School of Fundamental Sciences, Dankook University, Cheonan, Chungnam 330-714, South Korea b Department of Chemistry, College of Natural Sciences, Korea University, Chungnam 339-700, South Korea Received 20 September 2001; accepted 6 March 2002 This paper is dedicated to Professor Andrew Wojcicki on the occasion of his retirement from The Ohio State University
Abstract The solid state structure of the WCl2(OCH2CH2CH2CH2PPh2)2 (1) is determined by X-ray crystallography. Compound 1 ˚ , b /11.001(2) A ˚ , c /10.741(2) A ˚ , b / crystallizes in the space group C2 with the following unit cell parameters: a /16.474(3) A 127.21(3)8, and Z /2. The molecule is described as a distorted octahedral structure with two oxygen atoms trans , two chlorine atoms cis and two phosphorus atoms cis . Substantial p-bonding from alkoxide to tungsten is suggested by the relatively short ˚ . Stereochemistry of alkoxide ligand and substantial p-bonding is consistent with the fact that in distance of W/O with 1.816(11) A octahedral d2 systems, two p donors seek a mutual trans arrangement, regardless of the chelating /OCH2CH2CH2CH2PPh2 ligand. # 2002 Elsevier Science B.V. All rights reserved. Keywords: Alkoxide ligands; p-Bonding; X-ray crystallography
1. Introduction The complexes, d2 WCl2(OR)2L2 (OR /OCH2CF3, O(2,6-Ph2C6H3), O(C6H4X) where X /Me, Br and Ph, L /PMe2Ph, PMePh2) was reported to show different magnetism and stereochemistry depending on the identity of the substituent R [1,2]. In the case of aryl alkoxide [1b], steric hindrance of substituent was suggested to correlate the magnetism with the degree of O 0/W pbonding. In the case of aliphatic alkoxide [2], stereochemistry of the complex shows that alkoxides are trans each other, phosphines cis and chlorides cis , given that aryl alkoxide are all trans . It has been explained that rotational conformation about the W/O bonds in cis WCl2 would be more favorable to prevent electronic repulsion by providing wider range of dihedral angle between oxygen lone pair electrons not participating in p-bonding and chlorine regions. The common feature of these compounds was to show short W /O bond distances and establish some degree of alkoxide tungsten * Corresponding author. E-mail address: [email protected] (Y. Kim).
p-bonding. We report here solid state structure of the first example of the chelated aliphatic alkoxide analog, WCl2(OCH2CH2CH2CH2PPh2)2 (1) for WCl2(OR)2L2, which has trans , cis , cis stereochemistry.
2. Experimental Synthesis, analytical and spectroscopic characterization of WCl2(OCH2CH2CH2CH2PPh2)2 was previously reported [3a]. 2.1. Crystallographic details Suitable crystals of 1 were obtained by the slow diffusion of hexane into a methylene chloride solution of the complexes at room temperature (r.t.) and were mounted on a glass fiber. Diffraction measurements were made on an Enraf CAD4 automated diffractometer with graphite-monochromated Mo Ka radiation. The unit cell was determined by using search, center, index, and least-squares routines. F-scan technique was used for absorption corrections. The intensity data were
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Table 1 Crystal data and structure refinement for the compound 1 Empirical formula Formula weight Temperature ˚) Wavelength (A Crystal system Space group Unit cell dimensions ˚) a (A ˚) b (A ˚) c (A b (8) ˚ 3) V (A Z (g cm 3) Dcalc (g cm 3) Absorption coefficient (mm 1) F (000) Crystal size (mm) u Range for data collection (8) Index ranges Reflections collected/unique Completeness to 2u 51.94 Refinement method Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I 2s (I )] R indices (all data) Absolute structure parameter Largest difference peak and hole ˚ 3) (e A
C32H36Cl2O2P2W 769.30 293(2) K 0.71073 monoclinic C2 16.474(3) 11.001(2) 10.741(2) 127.21(3) 1550.4(5) 2 1.648 4.029 764 0.4 0.4 0.5 2.38 /25.97 0 h 11, 11 k 13, 11 l 13 2927/2388 [Rint 0.0446] 48.1% Full-matrix least-squares on F2 2388/1/196 1.112 R1 0.0605 a, wR2 0.1750 b R1 0.0611 a, wR2 0.1766 b 0.31(3) 2.490 and 1.434
a
R1 ajjFoj jFcjj (based on reflections with F2o 2sF2). wR2 [a[w (F2o F2c )2]/a[w (F2o)2]]1/2; w 1/[s2(F2o)(0.095P )2]; 2 2 2 P [max(Fo, 0)2Fc ]/3 (also with Fo 2sF2). b
corrected for Lorentz effects and for anisotropic decay. Equivalent data were then averaged to yield a unique set of intensities (Table 1). Each structure was solved by the application of direct methods using the SHELXL-86 program [4] and least-squares refinement using SHELXL-93 [5]. All non-hydrogen atoms were refined using anisotropic thermal parameters. All hydrogen atoms were located and refined using isotropic thermal parameters.
3. Results and discussion The reaction of WCl4(PPh3)2 with Ph2PCH2CH2CH2CH2OLi [3b] in thf leads to a green solid, which was recrystallized from thf, giving green crystals of WCl2(OCH2CH2CH2CH2PPh2)2 (1). The compound is stable to air, soluble in benzene and thf. The structure of 1 contains discrete, monomeric, neutral molecule. Final proof of the intramolecular coordination of the P ,O chelating group to the W metal in complex is provided by X-ray crystal structure analysis. As shown in Fig. 1, complex possesses a crystallographic disorder imposed by C2 symmetry. Thus, tethered atoms P(1), O(1), C(1),
Fig. 1. ORTEP drawing of WCl2(OCH2CH2CH2CH2PPh2)2 showing the atom-numbering scheme. Non-hydrogen atoms are represented by 50% probability thermal ellipsoids. Hydrogen atoms are omitted for clarity.
C(2), C(3), and C(4) atoms are related by crystallographic C2 rotation symmetry. As a consequence, two chlorine atoms are disordered by this axis so that the atomic positions designated by Cl(1)/Cl(1)* and Cl(2)/Cl(2)* are 50% occupied by chlorine atoms. The donor atoms surrounding the tungsten are at the apices of a distorted octahedron, in which the equatorial plane is occupied by the two cis chlorides and by the two phosphorus atoms of the bidentate ligand, with the alkoxide O1 atom trans to the alkoxide O(1)* atom (Fig. 1). The trans , cis , cis stereochemistry of present complex closely resemble that of WCl2(OCH2CF3)2(PMe2Ph)2 [1b]. Bond distances and angles of 1 are given in Tables 2 and 3. Data for the related d2, tungsten(IV) alkoxides are summarized in Table 4. The W /O ˚ of 1 are much shorter than 2.73 distance, about 1.82 A ˚ of single bond [6] and close to that of A Table 2 ˚ ) for the compound 1 Bond lengths (A W(1) O(1) W(1) Cl(2) W(1) Cl(1)* W(1) P(1) Cl(1) Cl(1)* Cl(2) P(1) Cl(2) Cl(2)* P(1) C(4)* O(1) C(1) C(2) C(3) C(4) P(1)* C(5) C(10) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16)
1.816(11) 2.42(2) 2.516(16) 2.522(4) 2.20(3) 1.53(2) 2.23(4) 1.825(17) 1.66(2) 1.41(5) 1.825(17) 1.42(3) 1.37(4) 1.39(4) 1.39(3) 1.17(11) 1.46(3)
W(1) O(1)* W(1) Cl(2)* W(1) Cl(1) W(1) P(1)* Cl(2) C(5) Cl(2) C(6) P(1) C(5) P(1) C(11) C(1) C(2) C(3) C(4) C(5) C(6) C(6) C(7) C(8) C(9) C(11) C(16) C(12) C(13) C(14) C(15)
1.816(11) 2.42(2) 2.516(16) 2.522(4) 1.39(3) 1.98(3) 1.799(19) 1.84(2) 1.85(5) 1.67(5) 1.41(3) 1.40(3) 1.36(5) 1.33(3) 1.44(4) 1.38(8)
Symmetry transformations used to generate equivalent atoms: * x1, y , z1.
M.-Y. Lee et al. / Inorganica Chimica Acta 334 (2002) 455 /458 Table 3 Angles (8) for the compound 1 O(1) W(1) O(1)* O(1)* W(1) Cl(2) O(1)* W(1) Cl(2)* O(1) W(1) Cl(1)* Cl(2) W(1) Cl(1)* O(1) W(1) Cl(1) Cl(2) W(1) Cl(1) Cl(1)* W(1) Cl(1) O(1)* W(1) P(1) Cl(2)* W(1) P(1) Cl(1) W(1) P(1) O(1)* W(1) P(1)* Cl(2)* W(1) P(1)* Cl(1) W(1) P(1)* Cl(1)* Cl(1) W(1) C(5) Cl(2) C(6) C(5) Cl(2) Cl(2)* C(6) Cl(2) Cl(2)* P(1) Cl(2) W(1) Cl(2)* Cl(2) W(1) Cl(2) P(1) C(4)* Cl(2) P(1) C(11) C(4)* P(1) C(11) C(5) P(1) W(1) C(11) P(1) W(1) O(1) C(1) C(2) C(2) C(3) C(4) Cl(2) C(5) C(6) C(6) C(5) C(10) C(6) C(5) P(1) C(7) C(6) C(5) C(5) C(6) Cl(2) C(9) C(8) C(7) C(9) C(10) C(5) C(16) C(11) P(1) C(11) C(12) C(13) C(13) C(14) C(15) C(11) C(16) C(15)
165.0(9) 89.7(7) 76.9(7) 103.1(6) 178.5(8) 90.5(6) 126.6(3) 51.9(7) 77.9(4) 85.6(5) 95.9(4) 94.5(4) 36.0(5) 142.6(4) 64.1(3) 45.3(12) 155.7(13) 111.7(9) 75.5(9) 62.5(5) 99.9(11) 146.0(12) 105.1(10) 112.4(5) 124.7(7) 114.7(17) 150.0(4) 90.1(17) 118.0(2) 122.2(15) 121.0(2) 44.7(11) 121.0(2) 119.0(3) 120.9(17) 117.0(3) 124.0(4) 118.0(2)
O(1) W(1) Cl(2) O(1) W(1) Cl(2)* Cl(2) W(1) Cl(2)* O(1)* W(1) Cl(1)* Cl(2)* W(1) Cl(1)* O(1)* W(1) Cl(1) Cl(2)* W(1) Cl(1) O(1) W(1) P(1) Cl(2) W(1) P(1) Cl(1)* W(1) P(1) O(1) W(1) P(1)* Cl(2) W(1) P(1)* Cl(1)* W(1) P(1)* P(1) W(1) P(1)* C(5) Cl(2) P(1) P(1) Cl(2) C(6) P(1) Cl(2) Cl(2)* C(5) Cl(2) W(1) C(6) Cl(2) W(1) Cl(2) P(1) C(5) C(5) P(1) C(4)* C(5) P(1) C(11) Cl(2) P(1) W(1) C(4)* P(1) W(1) C(1) O(1) W(1) C(3) C(2) C(1) C(3) C(4) P(1)* Cl(2) C(5) C(10) Cl(2) C(5) P(1) C(10) C(5) P(1) C(7) C(6) Cl(2) C(8) C(7) C(6) C(8) C(9) C(10) C(16) C(11) C(12) C(12) C(11) P(1) C(14) C(13) C(12) C(14) C(15) C(16)
76.9(7) 89.7(7) 54.9(10) 90.5(6) 126.6(3) 103.1(6) 178.5(8) 94.5(4) 36.0(5) 142.6(4) 77.9(4) 85.6(5) 95.9(4) 120.1(2) 75.8(12) 105.8(11) 125.3(15) 141.2(17) 172.3(14) 48.6(10) 107.1(9) 101.3(9) 68.4(8) 105.1(6) 131.2(11) 77.0(4) 106.5(18) 124.9(19) 55.6(11) 120.1(18) 138.9(17) 120.0(2) 121.0(3) 120.0(2) 118.7(19) 123.0(4) 117.0(4)
Symmetry transformations used to generate equivalent atoms: * x1, y , z1.
˚ ). This is consistent WCl2(OCH2CF3)2(PMe2Ph)2 (1.85 A with diamagnetic behavior of 1 in 1H NMR at r.t. which shows no contact shift. This suggested that two electrons are paired in non-degenerated orbitals derived from t2g orbitals due to strong O 0/W p-bonding. The W /Cl ˚ of 1 are comparable to distances, about 2.42 and 2.52 A those of diamagnetic WCl2(OR)2L2 (OR /OCH2CF3, O(C6H4Me), L /PMe2Ph, PMePh2) (about 2.48 and
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˚ , respectively). This W /Cl bond lengthening is 2.46 A general feature of enhanced filled-repulsions between paired d electrons and chloride lone pairs. The W /P ˚ of 1 are lengthened compared distances, about 2.52 A ˚ ) and with that of WCl2(OCH2CF3)2(PMe2Ph)2 (2.48 A ˚ ). comparable to WCl2(O(C6H4Me))2(PMePh2)2 (2.53 A This seems to be due to s-bonding ability of phosphine ligands. Although the W/O /C angles, 131.28 is smaller than those of the related tungsten(IV) alkoxide complexes, the W /O /C angles is enlarged over the tetrahedral angle. This suggests that complex 1 contains strong alkoxide tungsten p-bonding and is nearly 18 electron species. The seven-membered W /O /C /C /C / C /P ring is non-planar, with the dihedral angles between the planes defined by [W(1)/O(1)/C(13) / P(1)] and [O(1) /C(16) /C(14) /C(13)] being 56.0(8)8. The bite angle of O(1)/W(1) /P(1) is 94.5(4)8, suggesting cis arrangement of P,O atoms. In summary, the molecule of 1 is described as distorted octahedral structure with two oxygen atoms trans , two chlorine atoms cis and two phosphorus atoms cis . Substantial pbonding from alkoxide to tungsten is suggested by ˚. relatively short distance of W/O with 1.816(11) A The complex of WCl2(OCH2CH2CH2CH2PPh2)2 shows that stereochemistry of alkoxide ligands and substantial p-bonding are common features of the complexes, d2 WCl2(OR)2L2.
4. Supplementary material Tables of atomic coordinates, equivalent isotropic displacement parameters, anisotropic displacement parameters and torsion angles (three pages). Ordering information is given on any current masthead page.
References [1] (a) J.L. Kerschner, P.E. Fanwick, I.P. Rothwell, J.C. Huffman, Inorg. Chem. 28 (1989) 780; (b) S. Jang, L.M. Atagi, J.M. Mayer, J. Am. Chem. Soc. 112 (1990) 6413; (c) L.M. Atagi, J.M. Mayer, Angew. Chem., Int. Ed. Engl. 32 (1993) 439. [2] H. Rothfuss, J.C. Huffman, K.G. Caulton, Inorg. Chem. 33 (1994) 187.
Table 4 ˚ ) and angles (8) for related tungsten(IV) alkoxide complexes Summary of bond distances (A
W(O-2,6-Ph2-C6H3)2Cl2(PMe2Ph)2 [1a] W(O-4-Me-C6H4)2Cl2(PMePh2)2 [1b] W(OCH2CF3)2Cl2(PMe2Ph)2 [2] WCl2(Ph2PCH2CH2CH2CH2O)2 [This work]
˚) W O (A
˚) W Cl (A
˚) W P (A
W O C (8)
1.966(4) 1.848(5), 1.840(5) 1.844(5), 1.852(5) 1.816(11)
2.354(2) 2.471(2), 2.440(2) 2.4865(19), 2.4772(19) 2.42(2), 2.516(16)
2.551(2) 2.526(3), 2.534(3) 2.4892(19), 2.4810(20) 2.522(4)
140.4(4) 166.3(6), 171.7(5) 142.2(5), 144.8(5) 131.2(11)
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[3] (a) Y. Kim, M.-Y. Lee, Bull. Kor. Chem. Soc. 19 (1998) 1380; (b) Diphenyl-4-hydroxybutylphosphine was prepared according to the literature method [3c] and the bidentate ligand, Ph2PCH2CH2CH2CH2OLi was easily obtained by a lithiation of diphenyl-4-lithiumbutoxide phosphine; (c) A.Y. Garner, A.A. Tedeschi, J. Am. Chem. Soc. 84 (1962) 4734. [4] G.M. Sheldrick, in: G.M. Sheldrick, C. Kruger, R. Goddard (Eds.), Crystallographic Computing, vol. 3, Oxford University Press, London, 1985, pp. 175 /189.
[5] G.M. Sheldrick, in: H.D. Flack, L. Parkanyi, K. Simon (Eds.), Crystallographic Computing, vol. 6, Oxford University Press, Oxford, 1993, pp. 111 /122. [6] (a) K.W. Chiu, R.A. Jones, G. Wilinson, A.M.R. Galas, M.B. Hursthouse, K.M.A. Malik, J. Chem. Soc., Chem. Commun. (1981) 1204.; (b) R. Alvarez, E. Carmona, A. Galindo, E. Gutirrez, J.M. Marin, A. Monge, M.L. Poveda, C. Ruiz, J.M. Savariault, Organometallics 8 (1989) 2430.
Note
Solid state structure of WCl2(OCH2CH2CH2CH2PPh2)2 and pbonding ability of alkoxide in chelating P O ligand /
Myung-Young Lee a, Sang Ook Kang b, Youhyuk Kim a,* a
Department of Chemistry, School of Fundamental Sciences, Dankook University, Cheonan, Chungnam 330-714, South Korea b Department of Chemistry, College of Natural Sciences, Korea University, Chungnam 339-700, South Korea Received 20 September 2001; accepted 6 March 2002 This paper is dedicated to Professor Andrew Wojcicki on the occasion of his retirement from The Ohio State University
Abstract The solid state structure of the WCl2(OCH2CH2CH2CH2PPh2)2 (1) is determined by X-ray crystallography. Compound 1 ˚ , b /11.001(2) A ˚ , c /10.741(2) A ˚ , b / crystallizes in the space group C2 with the following unit cell parameters: a /16.474(3) A 127.21(3)8, and Z /2. The molecule is described as a distorted octahedral structure with two oxygen atoms trans , two chlorine atoms cis and two phosphorus atoms cis . Substantial p-bonding from alkoxide to tungsten is suggested by the relatively short ˚ . Stereochemistry of alkoxide ligand and substantial p-bonding is consistent with the fact that in distance of W/O with 1.816(11) A octahedral d2 systems, two p donors seek a mutual trans arrangement, regardless of the chelating /OCH2CH2CH2CH2PPh2 ligand. # 2002 Elsevier Science B.V. All rights reserved. Keywords: Alkoxide ligands; p-Bonding; X-ray crystallography
1. Introduction The complexes, d2 WCl2(OR)2L2 (OR /OCH2CF3, O(2,6-Ph2C6H3), O(C6H4X) where X /Me, Br and Ph, L /PMe2Ph, PMePh2) was reported to show different magnetism and stereochemistry depending on the identity of the substituent R [1,2]. In the case of aryl alkoxide [1b], steric hindrance of substituent was suggested to correlate the magnetism with the degree of O 0/W pbonding. In the case of aliphatic alkoxide [2], stereochemistry of the complex shows that alkoxides are trans each other, phosphines cis and chlorides cis , given that aryl alkoxide are all trans . It has been explained that rotational conformation about the W/O bonds in cis WCl2 would be more favorable to prevent electronic repulsion by providing wider range of dihedral angle between oxygen lone pair electrons not participating in p-bonding and chlorine regions. The common feature of these compounds was to show short W /O bond distances and establish some degree of alkoxide tungsten * Corresponding author. E-mail address: [email protected] (Y. Kim).
p-bonding. We report here solid state structure of the first example of the chelated aliphatic alkoxide analog, WCl2(OCH2CH2CH2CH2PPh2)2 (1) for WCl2(OR)2L2, which has trans , cis , cis stereochemistry.
2. Experimental Synthesis, analytical and spectroscopic characterization of WCl2(OCH2CH2CH2CH2PPh2)2 was previously reported [3a]. 2.1. Crystallographic details Suitable crystals of 1 were obtained by the slow diffusion of hexane into a methylene chloride solution of the complexes at room temperature (r.t.) and were mounted on a glass fiber. Diffraction measurements were made on an Enraf CAD4 automated diffractometer with graphite-monochromated Mo Ka radiation. The unit cell was determined by using search, center, index, and least-squares routines. F-scan technique was used for absorption corrections. The intensity data were
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Table 1 Crystal data and structure refinement for the compound 1 Empirical formula Formula weight Temperature ˚) Wavelength (A Crystal system Space group Unit cell dimensions ˚) a (A ˚) b (A ˚) c (A b (8) ˚ 3) V (A Z (g cm 3) Dcalc (g cm 3) Absorption coefficient (mm 1) F (000) Crystal size (mm) u Range for data collection (8) Index ranges Reflections collected/unique Completeness to 2u 51.94 Refinement method Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I 2s (I )] R indices (all data) Absolute structure parameter Largest difference peak and hole ˚ 3) (e A
C32H36Cl2O2P2W 769.30 293(2) K 0.71073 monoclinic C2 16.474(3) 11.001(2) 10.741(2) 127.21(3) 1550.4(5) 2 1.648 4.029 764 0.4 0.4 0.5 2.38 /25.97 0 h 11, 11 k 13, 11 l 13 2927/2388 [Rint 0.0446] 48.1% Full-matrix least-squares on F2 2388/1/196 1.112 R1 0.0605 a, wR2 0.1750 b R1 0.0611 a, wR2 0.1766 b 0.31(3) 2.490 and 1.434
a
R1 ajjFoj jFcjj (based on reflections with F2o 2sF2). wR2 [a[w (F2o F2c )2]/a[w (F2o)2]]1/2; w 1/[s2(F2o)(0.095P )2]; 2 2 2 P [max(Fo, 0)2Fc ]/3 (also with Fo 2sF2). b
corrected for Lorentz effects and for anisotropic decay. Equivalent data were then averaged to yield a unique set of intensities (Table 1). Each structure was solved by the application of direct methods using the SHELXL-86 program [4] and least-squares refinement using SHELXL-93 [5]. All non-hydrogen atoms were refined using anisotropic thermal parameters. All hydrogen atoms were located and refined using isotropic thermal parameters.
3. Results and discussion The reaction of WCl4(PPh3)2 with Ph2PCH2CH2CH2CH2OLi [3b] in thf leads to a green solid, which was recrystallized from thf, giving green crystals of WCl2(OCH2CH2CH2CH2PPh2)2 (1). The compound is stable to air, soluble in benzene and thf. The structure of 1 contains discrete, monomeric, neutral molecule. Final proof of the intramolecular coordination of the P ,O chelating group to the W metal in complex is provided by X-ray crystal structure analysis. As shown in Fig. 1, complex possesses a crystallographic disorder imposed by C2 symmetry. Thus, tethered atoms P(1), O(1), C(1),
Fig. 1. ORTEP drawing of WCl2(OCH2CH2CH2CH2PPh2)2 showing the atom-numbering scheme. Non-hydrogen atoms are represented by 50% probability thermal ellipsoids. Hydrogen atoms are omitted for clarity.
C(2), C(3), and C(4) atoms are related by crystallographic C2 rotation symmetry. As a consequence, two chlorine atoms are disordered by this axis so that the atomic positions designated by Cl(1)/Cl(1)* and Cl(2)/Cl(2)* are 50% occupied by chlorine atoms. The donor atoms surrounding the tungsten are at the apices of a distorted octahedron, in which the equatorial plane is occupied by the two cis chlorides and by the two phosphorus atoms of the bidentate ligand, with the alkoxide O1 atom trans to the alkoxide O(1)* atom (Fig. 1). The trans , cis , cis stereochemistry of present complex closely resemble that of WCl2(OCH2CF3)2(PMe2Ph)2 [1b]. Bond distances and angles of 1 are given in Tables 2 and 3. Data for the related d2, tungsten(IV) alkoxides are summarized in Table 4. The W /O ˚ of 1 are much shorter than 2.73 distance, about 1.82 A ˚ of single bond [6] and close to that of A Table 2 ˚ ) for the compound 1 Bond lengths (A W(1) O(1) W(1) Cl(2) W(1) Cl(1)* W(1) P(1) Cl(1) Cl(1)* Cl(2) P(1) Cl(2) Cl(2)* P(1) C(4)* O(1) C(1) C(2) C(3) C(4) P(1)* C(5) C(10) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16)
1.816(11) 2.42(2) 2.516(16) 2.522(4) 2.20(3) 1.53(2) 2.23(4) 1.825(17) 1.66(2) 1.41(5) 1.825(17) 1.42(3) 1.37(4) 1.39(4) 1.39(3) 1.17(11) 1.46(3)
W(1) O(1)* W(1) Cl(2)* W(1) Cl(1) W(1) P(1)* Cl(2) C(5) Cl(2) C(6) P(1) C(5) P(1) C(11) C(1) C(2) C(3) C(4) C(5) C(6) C(6) C(7) C(8) C(9) C(11) C(16) C(12) C(13) C(14) C(15)
1.816(11) 2.42(2) 2.516(16) 2.522(4) 1.39(3) 1.98(3) 1.799(19) 1.84(2) 1.85(5) 1.67(5) 1.41(3) 1.40(3) 1.36(5) 1.33(3) 1.44(4) 1.38(8)
Symmetry transformations used to generate equivalent atoms: * x1, y , z1.
M.-Y. Lee et al. / Inorganica Chimica Acta 334 (2002) 455 /458 Table 3 Angles (8) for the compound 1 O(1) W(1) O(1)* O(1)* W(1) Cl(2) O(1)* W(1) Cl(2)* O(1) W(1) Cl(1)* Cl(2) W(1) Cl(1)* O(1) W(1) Cl(1) Cl(2) W(1) Cl(1) Cl(1)* W(1) Cl(1) O(1)* W(1) P(1) Cl(2)* W(1) P(1) Cl(1) W(1) P(1) O(1)* W(1) P(1)* Cl(2)* W(1) P(1)* Cl(1) W(1) P(1)* Cl(1)* Cl(1) W(1) C(5) Cl(2) C(6) C(5) Cl(2) Cl(2)* C(6) Cl(2) Cl(2)* P(1) Cl(2) W(1) Cl(2)* Cl(2) W(1) Cl(2) P(1) C(4)* Cl(2) P(1) C(11) C(4)* P(1) C(11) C(5) P(1) W(1) C(11) P(1) W(1) O(1) C(1) C(2) C(2) C(3) C(4) Cl(2) C(5) C(6) C(6) C(5) C(10) C(6) C(5) P(1) C(7) C(6) C(5) C(5) C(6) Cl(2) C(9) C(8) C(7) C(9) C(10) C(5) C(16) C(11) P(1) C(11) C(12) C(13) C(13) C(14) C(15) C(11) C(16) C(15)
165.0(9) 89.7(7) 76.9(7) 103.1(6) 178.5(8) 90.5(6) 126.6(3) 51.9(7) 77.9(4) 85.6(5) 95.9(4) 94.5(4) 36.0(5) 142.6(4) 64.1(3) 45.3(12) 155.7(13) 111.7(9) 75.5(9) 62.5(5) 99.9(11) 146.0(12) 105.1(10) 112.4(5) 124.7(7) 114.7(17) 150.0(4) 90.1(17) 118.0(2) 122.2(15) 121.0(2) 44.7(11) 121.0(2) 119.0(3) 120.9(17) 117.0(3) 124.0(4) 118.0(2)
O(1) W(1) Cl(2) O(1) W(1) Cl(2)* Cl(2) W(1) Cl(2)* O(1)* W(1) Cl(1)* Cl(2)* W(1) Cl(1)* O(1)* W(1) Cl(1) Cl(2)* W(1) Cl(1) O(1) W(1) P(1) Cl(2) W(1) P(1) Cl(1)* W(1) P(1) O(1) W(1) P(1)* Cl(2) W(1) P(1)* Cl(1)* W(1) P(1)* P(1) W(1) P(1)* C(5) Cl(2) P(1) P(1) Cl(2) C(6) P(1) Cl(2) Cl(2)* C(5) Cl(2) W(1) C(6) Cl(2) W(1) Cl(2) P(1) C(5) C(5) P(1) C(4)* C(5) P(1) C(11) Cl(2) P(1) W(1) C(4)* P(1) W(1) C(1) O(1) W(1) C(3) C(2) C(1) C(3) C(4) P(1)* Cl(2) C(5) C(10) Cl(2) C(5) P(1) C(10) C(5) P(1) C(7) C(6) Cl(2) C(8) C(7) C(6) C(8) C(9) C(10) C(16) C(11) C(12) C(12) C(11) P(1) C(14) C(13) C(12) C(14) C(15) C(16)
76.9(7) 89.7(7) 54.9(10) 90.5(6) 126.6(3) 103.1(6) 178.5(8) 94.5(4) 36.0(5) 142.6(4) 77.9(4) 85.6(5) 95.9(4) 120.1(2) 75.8(12) 105.8(11) 125.3(15) 141.2(17) 172.3(14) 48.6(10) 107.1(9) 101.3(9) 68.4(8) 105.1(6) 131.2(11) 77.0(4) 106.5(18) 124.9(19) 55.6(11) 120.1(18) 138.9(17) 120.0(2) 121.0(3) 120.0(2) 118.7(19) 123.0(4) 117.0(4)
Symmetry transformations used to generate equivalent atoms: * x1, y , z1.
˚ ). This is consistent WCl2(OCH2CF3)2(PMe2Ph)2 (1.85 A with diamagnetic behavior of 1 in 1H NMR at r.t. which shows no contact shift. This suggested that two electrons are paired in non-degenerated orbitals derived from t2g orbitals due to strong O 0/W p-bonding. The W /Cl ˚ of 1 are comparable to distances, about 2.42 and 2.52 A those of diamagnetic WCl2(OR)2L2 (OR /OCH2CF3, O(C6H4Me), L /PMe2Ph, PMePh2) (about 2.48 and
457
˚ , respectively). This W /Cl bond lengthening is 2.46 A general feature of enhanced filled-repulsions between paired d electrons and chloride lone pairs. The W /P ˚ of 1 are lengthened compared distances, about 2.52 A ˚ ) and with that of WCl2(OCH2CF3)2(PMe2Ph)2 (2.48 A ˚ ). comparable to WCl2(O(C6H4Me))2(PMePh2)2 (2.53 A This seems to be due to s-bonding ability of phosphine ligands. Although the W/O /C angles, 131.28 is smaller than those of the related tungsten(IV) alkoxide complexes, the W /O /C angles is enlarged over the tetrahedral angle. This suggests that complex 1 contains strong alkoxide tungsten p-bonding and is nearly 18 electron species. The seven-membered W /O /C /C /C / C /P ring is non-planar, with the dihedral angles between the planes defined by [W(1)/O(1)/C(13) / P(1)] and [O(1) /C(16) /C(14) /C(13)] being 56.0(8)8. The bite angle of O(1)/W(1) /P(1) is 94.5(4)8, suggesting cis arrangement of P,O atoms. In summary, the molecule of 1 is described as distorted octahedral structure with two oxygen atoms trans , two chlorine atoms cis and two phosphorus atoms cis . Substantial pbonding from alkoxide to tungsten is suggested by ˚. relatively short distance of W/O with 1.816(11) A The complex of WCl2(OCH2CH2CH2CH2PPh2)2 shows that stereochemistry of alkoxide ligands and substantial p-bonding are common features of the complexes, d2 WCl2(OR)2L2.
4. Supplementary material Tables of atomic coordinates, equivalent isotropic displacement parameters, anisotropic displacement parameters and torsion angles (three pages). Ordering information is given on any current masthead page.
References [1] (a) J.L. Kerschner, P.E. Fanwick, I.P. Rothwell, J.C. Huffman, Inorg. Chem. 28 (1989) 780; (b) S. Jang, L.M. Atagi, J.M. Mayer, J. Am. Chem. Soc. 112 (1990) 6413; (c) L.M. Atagi, J.M. Mayer, Angew. Chem., Int. Ed. Engl. 32 (1993) 439. [2] H. Rothfuss, J.C. Huffman, K.G. Caulton, Inorg. Chem. 33 (1994) 187.
Table 4 ˚ ) and angles (8) for related tungsten(IV) alkoxide complexes Summary of bond distances (A
W(O-2,6-Ph2-C6H3)2Cl2(PMe2Ph)2 [1a] W(O-4-Me-C6H4)2Cl2(PMePh2)2 [1b] W(OCH2CF3)2Cl2(PMe2Ph)2 [2] WCl2(Ph2PCH2CH2CH2CH2O)2 [This work]
˚) W O (A
˚) W Cl (A
˚) W P (A
W O C (8)
1.966(4) 1.848(5), 1.840(5) 1.844(5), 1.852(5) 1.816(11)
2.354(2) 2.471(2), 2.440(2) 2.4865(19), 2.4772(19) 2.42(2), 2.516(16)
2.551(2) 2.526(3), 2.534(3) 2.4892(19), 2.4810(20) 2.522(4)
140.4(4) 166.3(6), 171.7(5) 142.2(5), 144.8(5) 131.2(11)
458
M.-Y. Lee et al. / Inorganica Chimica Acta 334 (2002) 455 /458
[3] (a) Y. Kim, M.-Y. Lee, Bull. Kor. Chem. Soc. 19 (1998) 1380; (b) Diphenyl-4-hydroxybutylphosphine was prepared according to the literature method [3c] and the bidentate ligand, Ph2PCH2CH2CH2CH2OLi was easily obtained by a lithiation of diphenyl-4-lithiumbutoxide phosphine; (c) A.Y. Garner, A.A. Tedeschi, J. Am. Chem. Soc. 84 (1962) 4734. [4] G.M. Sheldrick, in: G.M. Sheldrick, C. Kruger, R. Goddard (Eds.), Crystallographic Computing, vol. 3, Oxford University Press, London, 1985, pp. 175 /189.
[5] G.M. Sheldrick, in: H.D. Flack, L. Parkanyi, K. Simon (Eds.), Crystallographic Computing, vol. 6, Oxford University Press, Oxford, 1993, pp. 111 /122. [6] (a) K.W. Chiu, R.A. Jones, G. Wilinson, A.M.R. Galas, M.B. Hursthouse, K.M.A. Malik, J. Chem. Soc., Chem. Commun. (1981) 1204.; (b) R. Alvarez, E. Carmona, A. Galindo, E. Gutirrez, J.M. Marin, A. Monge, M.L. Poveda, C. Ruiz, J.M. Savariault, Organometallics 8 (1989) 2430.